Sciencemadness Discussion Board - Nitro Chitin

Nitro Chitin

sarinox - 12-9-2024 at 12:04

Hello Folks,

When I was a highschooler , I had the idea of synthesizing Nitro-chitin, knowing the fact that molecular structure of both Chitin and Cellulose looked similar to my highschooler eyes!

My questions are:

1-Has anyone already tried to synthesize Nitro Chitin?
2- Is it even possible?

I had collected nail clips and then put the nail clips inside a mixture of Sulfuric and Nitric acid ( not fuming Nitric acid just Nitric acid with concentration of 65% ish) the nail clips turned yellow but they did not burn like Nitro Cellulose - Yes they burn but like a normal nail clip would burn!-, my other attempts failed as well. Now after almost two decades I still am searching for the answer to this question that's why I reached out to you guys.

I think maybe I should first extracted Chitin from nail clips ( which I don't know how is it done till this day!) and then tried to turn it to Nitro Chitin.

So, if you know how to separate Chitin from finger nails I would appreciate it if u let me know.

-Sarinox

UndermineBriarEverglade - 12-9-2024 at 14:38

Looks like your high school hunch was right. Liu, J. (2019). Chitin and Algae Nitrates. Nitrate Esters Chemistry and Technology, 599–608. doi:10.1007/978-981-13-6647 talks about it. The references might be helpful.

Quote:

Since the surface of raw chitin is wrapped with lipids, general chemical reagents cannot penetrate the surface of chitin. It is required to remove the surface materials such as pectin, carbohydrates, and lignin via chemical treatment before the preparation of chitin nitrates.

They detail a purification process where chitin is soaked in dilute HCl at 130C for 2-3h, washed with alkali and "saponification agent" below 130C for 6h.

Quote:

it was impossible to nitrate the chitin with a commonly mixed acid containing sulfuric acid because the chitin was decomposed by the strong oxidation capability of the sulfuric acid.

If I'm reading this right, it can be nitrated either with WFNA or a mix of nitric and phosphoric acids.

Sir_Gawain - 12-9-2024 at 15:13

Even if it would work, only the very outer surface of the nail chips would be nitrated because the acid cannot penetrate very deeply.

j_sum1 - 12-9-2024 at 15:28

I would try cicada shells as a starting material over toenails.

(There is a sentence that has never been written before.)

sarinox - 12-9-2024 at 22:36

Quote:

They detail a purification process where chitin is soaked in dilute HCl at 130C for 2-3h, washed with alkali and "saponification agent" below 130C for 6h.

Thanks for the info.

Quote:

it was impossible to nitrate the chitin with a commonly mixed acid containing sulfuric acid because the chitin was decomposed by the strong oxidation capability of the sulfuric acid.

Well, I knew I was doing something wrong! But the idea of turning nail clips into something like Nitro Cellulose was interesting back then!

Quote:

If I'm reading this right, it can be nitrated either with WFNA or a mix of nitric and phosphoric acids.

I did not have access to WFNA ( should I make it myself?) is it gonna be tricky?

sarinox - 12-9-2024 at 22:39

Quote: Originally posted by Sir_Gawain

Even if it would work, only the very outer surface of the nail chips would be nitrated because the acid cannot penetrate very deeply.

I think you are 100% correct, it kind of looked like it did work (or maybe my brain forced me to see it that way!) it seemed the outer shell burned better but the inner substances were not touched by the acid mixture and they burned just like a normal nail clip (or as I said it could be my forced perception!)

sarinox - 12-9-2024 at 22:41

Quote: Originally posted by j_sum1

I would try cicada shells as a starting material over toenails.

(There is a sentence that has never been written before.)

Do u have Cicada shells in abundant? I think you could use Shrimp shells as well. (don't know how by the way)

And I would be supper happy if you share your progress :-)

Sir_Gawain - 12-9-2024 at 22:42

You can make WFNA by distilling nitric acid with sulfuric acid. The distillate will likely have some nitrogen dioxide dissolved in it, which can be removed by cooling to below 0°C and adding a few drops of hydrogen peroxide.

Laboratory of Liptakov - 13-9-2024 at 22:40

In any case, it is necessary to use the finest and driest possible powder of the starting substance for nitration / esterification.... :cool:

DraconicAcid - 14-9-2024 at 13:15

Aren't toenails made of keratin (a protein), not chitin?

bnull - 14-9-2024 at 14:44

Quote: Originally posted by DraconicAcid

Aren't toenails made of keratin (a protein), not chitin?

Yes.

Chitin: invertebrates and fungi; keratin: vertebrates.

EdricoRojo - 19-9-2024 at 16:47

Well, I wasn't expecting Chitin to be mentioned in reference to energetics. I have been doing rudimentary newbie research into another topic (dust control polymers) and was planning on doing tests with Chitosan. Please excuse the rookie stumblings, but looking at the Chitosan molecule compared to the Chitin and Cellulose. It may be suitable for your task of nitration. I know it is water soluble. It may be able to be nitrated more easily then just Chitin. Just a thought, hopefully it isn't absolutely stupid lol.

sarinox - 23-9-2024 at 09:12

Quote: Originally posted by DraconicAcid

Aren't toenails made of keratin (a protein), not chitin?

Indeed you are right.

However, back in the day I had no access to good resources. I had access to a book which contained figures of molecular structures of Chitin and Cellulose. Unfortunately I had heard from a teacher that toe nails are made of chitin and this mistake stuck in my mind and I thought : "hmmm, why cannot we make Nitro chitin if its molecular structure has similarities with cellulose? can we use toe nails as a source of chitin?"

Anyway Now I decided to share this idea! (Nitrochitin) :-)

sarinox - 23-9-2024 at 09:14

Quote: Originally posted by j_sum1

I would try cicada shells as a starting material over toenails.

(There is a sentence that has never been written before.)

@jsum_1 is there any updates?

Axt - 29-9-2024 at 11:22

There has been a few investigations on using chitin like cleaving into the monomer to give a tetranitrate, and deacetylation to chitosan followed by nitration. Chitosan is easily commercially available. I feel sure I had reference to a nitramine derivative of chitosan too but I'm failing to find it now.

Direct nitration will result in an acid salt of an amino nitrate ester. These are not stable though, it's of novel interest but not of a practical one.

MineMan - 30-9-2024 at 14:57

Quote: Originally posted by Axt

There has been a few investigations on using chitin like cleaving into the monomer to give a tetranitrate, and deacetylation to chitosan followed by nitration. Chitosan is easily commercially available. I feel sure I had reference to a nitramine derivative of chitosan too but I'm failing to find it now.

Direct nitration will result in an acid salt of an amino nitrate ester. These are not stable though, it's of novel interest but not of a practical one.

Whoa! Your back! Haven’t seen you since before 2010!

Axt - 2-10-2024 at 17:17

Here's the references.

In summary,

1. Direct nitration of chitin isn't entertained, rather its cleaved into a monomer via acid hydrolysis. Then subjected to acetic anhydride / nitric acid nitration to afford the tetranitrate. Its comparable in properties to microcrystalline nitrocellulose.

2. Deacetylation to chitosan was done via heating in NaOH. Nitrate salts and perchlorate salts of this were stable. When nitrated via 100% HNO3 chitosan gave dinitrochitosan nitrate salt, treatment with perchloric acid gave the perchlorate salt. These salts of nitric esters are not stable, with the perchlorate salt detonating in storage.

3. Acetic anhydride / nitric acid nitration of chitosan affords the dinitrate nitramine which has slightly superior properties than nitrocellulose, though lower thermal stability.

Hello Mineman, presumably you've changed your name. Yes, I think I've maybe logged in 4 times in the last 15 years heh, you guys better not give me the bug again.

Attachment: Chitin nitration.zip (3.8MB)
This file has been downloaded 106 times

MineMan - 3-10-2024 at 15:06

Thank you for the reply Ax!

It’s Chitostan I am most interested in.

I don’t find it surprising that the perchlorate salt is unstable.

Never changed my name. I don’t know what you mean by “bugs”. I sent you a DM explaining who I am since you have been gone since I joined. Perhaps you can kindly check it and reply.

Here is a paper or two by Klapotke. Not sure if you have read them?

https://www.mdpi.com/2227-9717/11/11/3060

https://link.springer.com/article/10.1007/s10570-023-05200-0